Manufacture and production of artificial threads from viscose



y 14, 1953 J. WHARTON ETAL 2,645,555

MANUFACTURE AND PRODUCTION OF ARTIFICIAL THREADS FROM YISCOSE Filed Jan. 27, 1949 2 Sheets-Sheet l lnvenfors John l/l fmnan Rona/d Berfmm H0// By their attorneys 20 M M M ly 1953 J\. WHARTON ETAL MANUFACTURE AND PRODUCTION OF ARTIFICIAL THREADS FROM VISCOSE Filed Jan. 27, 1949 2 Sheets-Sheet 2 FIG-2..

Mme/wars Jo/m W/mnon Rona/0 Barf/0m Ha By their aflomeys Patented July 14, 1953 MANUFACTURE AND PRODUCTION OF'ARTI- FICIAL THREADS FROM VISCOSE John Wharton and Ronald Bertram Hall; Coventry, England, assignors to Courtaulds Limited', London, England, a British company Application. January 27, 1949, Serial No. 73,136

In Great Britain February 18, 1948 11 Claims.

This invention relates to the manufacture and the production of artificial. threads filaments, yarns and the like. hereinafter referred to as threads, from viscose.

In the production oi artificial threads from viscose, viscose is, extruded through a jet into a coagulating bath containing sulphuric acid and one or more metallic salts. The threads are withdrawnfrom the coagulating bath and passed by means. of thread guides over one or more godets, or the threads are. passed on to. one or more. thread-advancing reels where they are treated withv processing. liquids. Insoluble substances are formed, by the reaction which takes. place during the coagulation; andv subsequent. treatment of. the. thread and these. substances are carried away by the. thread and. tend, to form hard deposits on thread guides, godets and thread-advancing reels.

It has already been proposed in U- S. Letters Patent. specification 1810.. 2,125,031. to add. tothe spinning bath or to the spinning solution anorganic substance the molecule of which has. a. surface-active cation. derived. from an, organic base substituted by an aliphatic, chain of high molecular weight, in order to. inhibit the fouling of the jets. It has also been: proposed in. the specification. of U. S. Letters Patent No 2,394,519 to. ex-- trude viscose. into, an acidic. coagulating liquid containing an emulsified petroleum 011,. which. is, insoluble in the liquid and forms. a sludge with impurities in the coagulating liquid and tends to, inhibit the, formation of harmful deposits not only in and upon the jets but also upon other parts of the apparatus;

The object of the present invention isto improve the production ofartificia-l' threads from viscose by preventing the formation of rock-like deposits and incrusta-tions on thread guides, godets or thread-advancing reels and to effect lubrication of the thread during its manufacture.

The present. invention consists of; aprocess; for

the production of artificial threads. f-rom viscose by extruding: the viscose into a coagulating bath; containing an acid and one or more; metallic salts wherein the thread after leaving the coagulating bath is treated with an oil haying dissolved in The presentihvention may conveniently be 5 fill used in a process in which the'threads after leaving the coagulating bath are stretched whilst immersed in a bath of hot dilute acid, for example, as described in U. S. Letters Patent specification No. 2,192,074. With such processes the treatment with the oilhaving dissolved in it the oil-soluble cation-active compound is preferably applied before the thread passes into the bath of hot dilute acid.

When carrying out. the process of the present invention the oil having dissolved in it the oilsoluble cation-active compound is preferably allowed to drip onto the thread while it. is passing over a godet or a thread-advancing'reel. V

In practice for economic reasons and for general usefulness the oilemployed is a mineral oil such as that known. as white oil, the term 0' is used. in this specification tocover any organic liquid which may be used for the lubrication of solid surfaces, for exampla vegetable oils, such as olive oil or cotton seed oil and animal oils such as sperm oil. It isdesirable-that the cationactive com-pound shouldbe soluble in the oil being employed. to. such an extent that a clear solution is obtainedbut total solubility is. not essential provided the oil and cation-active. compound may be delivered. to the machine without separation; It; will therefore: be necessary to select a cation-active compound. according to the oil being. used;v The-following classes of cationactive compounds will normally be found sufliciently soluble inthe mineral oil which will be commonly used in practice.

1., Condensation products of the general formula R..C.O.(NHC2H4):n-NH2 in which R is a long chain hydrophobe: group; with not less than 10. carbon. atoms in: the. chain and n is an integer of 1 to 5.. These; compounds are obtained by condensing a long chain; fatty acid with. an aliphatic poly'amine; for example bycondensing 1 mol of oleic, stearic or palmitic acid or a. mixture ofthesev acids-with. I mol of diethylene triamine, triethyl'ene tetramine OrpentaethyIene hexamineon a mixture of these pol yamines, at

aboutxi8'0 centigradefor three hours.

2.Condensationproductsof the general for-- mul'a:

R.,G:O.(NH-CzH-4).NH -X in which R is alongchain hydrophobe group with; not less; than 10: carbon atoms in the chain, 11; is an' integer'of I to 5; R; Rf" are al'kylgroups,

for example methyl or ethyl groups; and X'is air obtained by reacting such condensation products with an alkylene oxide, for example ethylene oxide providing that the ethylene oxide is restricted so that the oil-soluble properties are retained. 4. Condensation products obtained by reacting a long chain aliphatic primary amine, for ex-' ample octadecylamine, with an alkylene oxide,

for example ethylene oxide, until a product is formed which is just dispersible in water.

5. Condensation products obtained by reacting a long chain aliphatic primary amine with ethyleneoxide and alkylating the product obtained by treatment, for example, with dimethyl or diethyl sulphate. Th general formula of the condensation products obtained is:

R! R.T .CzH4. (C2H40)OH.

in which R is a long chain hydrophobe group with not less than 10 carbon atoms, R. and R are alkyl groups, X is an anion, for example Br", ESQ? or CHsCOO and n is an integer of 2 to 20 according to the chain length of R.

The most effective oil-soluble cation-active compounds for carrying out the present invention are those which will form emulsions when the oil containing the cation-active compound is shaken up with diluteaqueous solutions containing sulphuric acid and one or more metallic salts.

In the production of artificial threads from viscose of high denier, for example a thread of 1180 denier 500 filament, the formation of rocklike deposits on those parts of the spinningmachine with which the threads come into contact immediately after leaving the coagulating bath is particularly rapid so that treatment of the thread on the first godet or thread-advancing device with oil having dissolved in it an oilsoluble cation-active compound in accordance with the present invention is of particular value.

The process of the present invention is particularly useful in the continuous spinning process in which the thread is withdrawn from the coagulating bath and passed over one or more threadadvancing reels in a number of helical turns, the.

7 would have a deleterious action on the thread as well as necessitating frequent and arduous cleaning operations.

The accompanying diagrammatic drawings further illustrate the process of the present invention:

Figure 1 represents part of a continuous spinning machine and,

, Figure 2 represents part ,of a centrifugal spinning machine.

Referring to Figure 1, viscose is extruded from the jet 1 from the supply pipe 2 into the coagulating bath 3 toform the thread ii. The coagulating bath 3 may conveniently contain sulphuric acid'and one or more metallic salts. The thread leaving the coagulating bath 3 passes upwards to the thread-advancing device 5 over which it travels in a number of advancing helical turns. Oil having dissolved in it an oil-soluble cationactive compound is allowed to drip on to the thread 4 from the distributor 6 While the thread is passing over the thread-advancing device 5. On reaching the discharge end of thread-advancing device 5 the thread passes vertically downwards to thread-advancing device '4 and thence'to thread-advancing devices 8, 9 and [0, over each of which it travels in a number of advancing helicalturns. While the thread is travelling over thread-advancing devices l, 8 and 9 it may be subjected to treatment with one or more processing liquids for example, washing, desulphurising and bleaching liquids, the processing liquids being supplied by the distributors H, ifiand l5 and the used processing liquids being collected in drip pans l2, l4 and it. The threadadvancing device is supplied internally with steam for heating and drying the thread. The dried thread is collected on a holder H by the cap spinning device I8. The dripping of oil having dissolved in it an oil-soluble cation-active compound onto the thread travelling on threadadvancing device 5 prevents the formation of rock-like deposits on thread-advancing devices 5, i, 8, 9 and NJ, so that the machine can be operated for long periods without stoppages for cleaning. I

Referring to Figure 2, viscose is extruded from the jet 20 from the supply pipe 2| into the coagulating bath 22 to form the thread 23. The coagulating bath may. conveniently contain sulphuric acid and one or more metallic salts. The thread 23 leaving the coagulating bath 22 passes on to the godet'zd by means of thread-guide 24. Oil having vdissolved in it an oil-soluble cation-active compound is allowed to drip from the distributor 26 onto the threadpassing over the godet 25. The thread leaving godet 25 passes up to godet 2'5 and is then guided by the spinning funnel 28 into the rapidly rotating box 25) where the thread is collected in the form of a cake. The godets 25, 2'1, thread-guide 24 andspinning funnel 28 remain free from rock-like deposits.

The addition of less than '10 per cent on the weight of oil of an oil-soluble cation-active compound a-ccording to the process of the present invention gives the thread an affinity for the oil so that the oil is retained on the thread in sufficient quantity to lubricate the thread during subsequent treatment. The oil retained on the thread may be sufficient to render the usual soaping or finishing treatment unnecessary.

The present invention therefore prevents the formation or rock-likedeposits on threa'd'guides, godets and thread-advancing reels and effects lubricationof the thread while economising in the quantity of oil used.

, Theiollowing examples illustrate the present I with 1 mol of diethylene triamine.

invention, the percentages: and parts being by weight: f i Example-.1

Viscose is.- extruded through aj multi-hole jet into a coagulating bath containinglil per cent of sulphuric acid; 1c percent ofsod-ium sulphate and 1 per cent of zinc sulphate. The thread is withdrawnfrom the coagulating bath andtpa'ssed onto the delivery end of a thread-advancing reel where it is immediately treated by dripping on it at the rate of 0.25 cm. per minute a per cent solution in mineral oil of a cation-active compound obtained by condensing 1 mol of oleic acid with 1 mol of triethylene tetramine at 180 centigrade for 3 hours. The thread is then sprayed with a solution containing 1.5 per centof sulphuric acid, 5 per cent of sodium sulphate and 0.2 per cent of zinc sulphate. The thread reaches the discharge end of the reel and then passes on to a second thread-advancing reel. The thread has retained suflicient oil to lubricate the second reel and to prevent formation of hard deposits on both reels.

Emample 2 Viscose thread leaving the coagulating bath is passed on to a thread-advancing reel where it is sprayed at the rate of 0.2 cm. per minute with a 5 per cent solution in olive oil of a cation-active compound obtained by alkylating at room tem perature with 1 mol of dimethyl sulphate the condensation product of 1 mol of palm kernel oil The thread is then sprayed with a solution containing 2 per cent of sulphuric acid, 4.2 per cent of sodium sulphate and 0.5 per cent of zinc sulphate. The treatment with the oil containing the cationactive compound prevents harmful deposits of sulphur impurities forming on the reel since the oil retained. by the thread lubricates the reel. The thread obtained after washing is soft and pliable and does not require soaping.

Example 3 Viscose rayon thread of 1180 denier, 500 filaments is withdrawn from the coagulating bath and passed round a godet. A 3 per cent solution in mineral oil of a cation-active compound obtained by condensingl part of stearyl ethanolamide with 2 parts of ethylene oxide is dripped on to the thread passing over the godet at the rate of 0.2 cm. per minute. The thread is then passed through a hot dilute acid bath containing from 0.5 to 4 per cent of sulphuric acid, from 1 to 12 per cent of sodium sulphate and from 0. to 1.5 per cent of zinc sulphate and subjected to a stretching as described in U. S. Letters Patent specification No. 2,192,074. The thread retains sufiicient oil, even after its'passage through the stretching bath to prevent deposits on the thread guides and godets over which the thread is passed after leaving the stretching bath.

What we claim is:

1. A process for the production of artificial threads from viscose by extruding viscose into a coagulating bath containing sulphuric acid and at least one metallic sulphate including as the first step after the thread leaves the coagulating bath, a step of treating the thread with a solution consisting of an oil selected from the group consisting of mineral oils, vegetable oils and animal oils and a cation-active compound soluble in the oil.

'A process: a'stclaimedi in. claim 1. whereim the; oil-soluble cation-active compound is a cond'ensation product obtained by" condensing a long chain: fatty'i'aci'cl'wiith an. aliphatic polyamine.

.3. A process as claimed in claim 1 wherein the oil-solublecation-active compound is the condensation product obtained by" reacting a long chain fatty acid having not less than 10 carbon atoms'ifrthe chain with an alkanolamine.

41A process as claimed in claim. 1 wherein the oil-soluble cation-active compound is the condensation product obtained by reacting a long chain aliphatic primary amine with an alkylene oxide until a water-dispersible product is found.

5. A process as claimed in claim 1 wherein the oil-soluble cation-active compound is oleyl polyamide obtained by condensing oleic acid with triethylene tetramine.

6. A process as claimed in claim 1 wherein the oil-soluble cation-active compound is oleyl ethanolamide.

7. A process for the production of artificial threads from viscose by extruding viscose into a coagulating bath containing sulphuric acid and at least one metallic sulphate, including as the first step after the thread leaves the coagulating bath, a step of treating the thread with a solution consisting of mineral oil and a cation-active compound soluble in the oil.

8. A continuous process for the production of artificial threads from viscose by extruding viscose into a coagulating bath containing sulphuric acid and at least one metallic sulphate and subjectin the thread thus formed without any break to a series of treatment liquids and to drying and winding onto a package, including as the first step after the thread leaves the coagulating bath, a step of treating the thread with a solution consisting of an oil selected from the group consisting of mineral oils, vegetable oils and animal oils and a cation-active compound soluble in the oil.

9. A continuous process for the production of artificial threads from viscose by extruding viscose into a coagulating bath containing sulphuric acid and at least one metallic sulphate and subjecting the thread thus formed without any break to a series of treatment liquids and to drying and winding onto a package, including as the first step after the thread leaves the coagulating bath, a step of treating the thread with a solution consisting of mineral oil and a cation-active compound soluble in the oil.

10. A process for the production of artificial threads from viscose by extruding viscose into an aqueous coagulating bath containing sulphuric acid and at least one metallic sulphate including the step of treating the thread after it leaves the coagulating'bath with a solution consisting of an oil selected from the group consisting of mineral oils, vegetable oils and animal oils and a cation-active compound soluble in the oil and treating the thread subsequently with an aqueous processing liquid containing sulphuric acid and at least one metallic sulphate.

7 1 8i stietchirrg th thread subsequently in a-hot dilute Number I 1 Name Date acid bath. I 2,214,352 Schoeller et a1. Sept. 10, 1940 1 JOHN WHARTON; 1 2,309,072 Burkholder Jan. 19, 1943 'RONALD BER'IRAM HALL. 2,329,086 1 Robinso n et a1. Sept. 7, 1943 :Bgferences C1ted.1n the file of thls patent vFOREICm. PATENTS UNITED STATES PATENTS Number Country Date Number j. I Name Date 546,051 "'Great' Britain June 25, 1942 1,970,578: Schoeller et a1. Aug. 21, 1934 10 2,125,031 Polak et a1 July 26, 1938 5 2345,5705" 'B1e y Apr. 4, 1944 

1. A PROCESS FOR THE PRODUCTION OF ARTIFICIAL THREADS FROM VISCOSE BY EXTRUDING VISCOSE INTO A COAGULATING BATH CONTAINING SULPHURIC ACID AND AT LEAST ONE METALLIC SULPHATE INCLUDING AS THE FIRST STEP AFTER THE THREAD LEAVES THE COAGULATING BATH, A STEP OF TREATING THE THREAD WITH A SOLUTION CONSISTING OF AN OIL SELECTED FROM THE GROUP CONSISTING OF MINERAL OILS, VEGETABLE OILS AND ANI- 